Azo dyes having a triazolium diazo component radical with a fused cycloalkyl ring

ABSTRACT

K is a coupling component radical, A is an anion, and N IS 1 TO 10, THE PRODUCTION THEREOF AND THE USE THEREOF IN DYEING AND PRINTING SYNTHETIC POLYMER TEXTILE SUBSTRATES AND DYEING PLASTICS IN THE MASS, LEATHER AND PAPER.   wherein R1 is alkoxy, cycloalkyl or substituted or unsubstituted alkyl or alkenyl, R2, R3, R4, R5, R6 and R7, independently, are hydrogen, alkyl, cycloalkyl or phenyl,   Disclosed are basic azo dyes, free from water solubilizing groups, of formula I,

United States Patent [1 1 Henzi Dec. 16, 1975 AZO DYES HAVING ATRIAZOLIUM DIAZO COMPONENT RADICAL WITH A FUSED CYCLOALKYL RING [75]Inventor: Beat Henzi, Neuallschwil,

Switzerland [30] Foreign Application Priority Data Aug. 10, 1972Switzerland 11843/72 [52] US. Cl 260/146 R; 260/146 D; 260/147',

[51] Int. Cl. C09B 29/36; DO6P 1/41 [58] Field of Search 260/146 R, 146D, 147,

[56] References Cited UNITED STATES PATENTS 3,102,878 9/1963 Baumann eta1 260/157 X 3,133,910 5/1964 Baumann et al 260/146 R 3,417,075 12/1968Mingasson et a1. 260/157 X 3,573,272 3/1971 Kaupp et a1. 260/146 D3,585,182 6/1971 Straley et a1 260/158 X 3,595,852 7/1971 Hahn et a1.260/158 3,654,259 4/1972 Iizuka et a1. 260/146 R X 3,679,656 7/1972lizuka et a1. 260/146 R X 3,691,148 9/1972 Peter et a1. 260/1583,717,625 2/1973 Peter et a1, 260/158 3,763,140 10/1973 Entschel et a1.260/157 X 3,770,719 11/1963 Fisher et a1. 260/158 Primary ExaminerFloydD. Higel Assistant ExaminerC. F. Warren Attorney, Agent, or FirmGeraldD. Sharkin; Richard E. Vila; Melvyn M. Kassenoff [57] ABSTRACT Disclosedare basic azo dyes, free from water solubilizing groups, of formula 1,

I R, /[M

*c A6 P 16y R,

C), T R5 R, R,

wherein R is alkoxy, cycloalkyl or substituted or unsubstituted alkyl oralkenyl, R R R R R and R independently, are

hydrogen, alkyl, cycloalkyl or phenyl,

| Bis=NC=N- or=N--N=C- K is a coupling component radical, A is an anion,and n is 1 to 10, the production thereof and the use thereof in dyeingand printing synthetic polymer textile substrates and dyeing plastics inthe mass, leather and paper.

26 Claims, No Drawings AZO DYES HAVING A TR IAZOLIUM DIAZOCOMPONENTRADICAL A FUSED CYCLOALKYL RING IMPROVEMENTS IN OR RELATING TOORGANIC COMPOUNDS The present invention relates to basic azo dyes, freefrom sulphonic acid groups, their production and use.

The invention provides basic azo dyes of formula I,

A6 vvi in which R, signifies an unsubstituted or substituted alkyl oralkenyl radical, which alkyl and alkenyl radicals contain up to 4 carbonatoms, an alkoxy radical of 1 to 4 carbon atoms or a cycloalkyl radicalcontaining to 7 ring carbon atoms,

each of R R R R R andR which may be the same or different, signifies ahydrogen atom, an unsubstituted (C .alkyl, (C cycloalkyl or phenylradical, y

B signifies a radical of formula II or IIa,

in which R2, R3, R4, R5, R6, R, and B are as defined above,

with a compound of forumla IV,

in which R, is as defined above, and A signifies a radical convertibleto the anion A as defined above, or by reacting an R yielding epoxide orsaturated or unsaturated acid amide with a compound of formula III, asdefined above, in the presence of an acid HA.

'The quaternation may be accomplished in conventional manner; forexample, the reaction may be carried out in an inert solvent, in anaqueous suspension 5 or, if the quaternating agent is liquid under thereaction conditions, in the absence of solvent using an excess of thequaternating agent. Where necessary, the reaction may be carried out atelevated temperatures and in a buffered medium.

Suitable quaternating agent of formula IV include alkyl halides, suchas, methyl or ethyl chloride, bromide or iodide, alkylsulphates, such asdiinethylsulphate or benzyl chloride. Other quaternating agents includea mixture of acrylic acid amideand hydrohalides, such as CI-I =CHCONI-I/I-ICI, chloracetic acid amide, epoxides, such as ethylene or propyleneoxide or epihalohydrin in the presence of an acid of formula HA.

In the compounds of formula I, K may be a radical of a couplingcomponent of the benzene or naphthalene series, such as amino or hydroxybenzenes or naphthalenes, of the heterocyclic series, such as pyrazoloneor arninopyrazole series, indole or carbazole series, advantageously2-phenylindole series, barbituric acid series, or of the aliphaticseries such as the alkane, alkene or alkyne series which contain anacitve methylene group suitable for coupling, for example, acyl aceticacid alkylamides, malonic acid or malonic acid nitrile derivatives.

In the compounds of formula I, K may, for example, be a radical of theformula in which,

each of R and R which may be the same or different, signifies a hydrogenatom, an unsubstituted alkyl, phenyl or cycloalkyl radical, analkylphenyl radical, or an alkyl radical substituted by a halogen atom,a phenyl, alkoxy, phenoxy, phenylaminocarbonyloxy, alkylcarbonyloxy,alkoxycarbonyl, hydroxy, phenylcarbonyloxy or cyano group, with theproviso that when one of R and R signifies a cycloalkyl, phenyl oralkylphenyl radical the other has a significance other than cycloalkyl,phenyl or alkylphenyl, which alkyl radicals or moieties in such radicalscontain 1 to 4 carbon atoms, which alkoxy moieties in such radicalscontain 1 to 4 carbon atoms and which cycloalkyl radical contains 5 to 7carbon atoms, preferably cyclohexyl,

or R and R together with the nitrogen atom to which they are bonded forma pyrrolidine, piperidine, morpholine or piperazine ring,

R signifies a hydrogen atom, an alkyl radical of l to 4 carbon atoms,preferably, methyl or ethyl,

R signifies an alkyl radical of l to 4 carbon atoms,

preferably a methyl radical, or a radical,

R signifies a hydrogen atom or an alkyl radical of l to 4 carbon atoms,preferably an ethyl radical,

R signifies a hydrogen atom or an alkyl radical of l to 4 carbon atoms,preferably methyl,

R signifies a hydroxy, amino, phenylamino or alkylsubstitutedphenylamino radical, preferably, dimelected from halogen atoms, alkyl of1 to 4 carbon atoms and alkoxy of 1 to 4 carbon atoms,

the rings Z Z and Z may be further unsubstituted or may be furthersubstituted by up to two substituents selected from halogen atoms,nitro, amino, cyano, thiocyano, hydroxyl, alkyl, alkoxy, trifluoroalkyl,trichloroalkyl, phenyl, phenoxy, alkylamino, dialkylamino, alkanoyl,alkanoyloxy, alkanoylamino, alkylsulphonyl, phenylsulphonyl,aminosulfonyl (sulfamoyl), alkylsulphonylamino, phenylsulphonylaminogroups, which alkyl and alkoxy groups or moieties in such groups contain1 to 4 carbon atoms, preferably the rings Z Z Z Z and Z independently,are further unsubstituted or are further substituted by an alkyl of l to4 carbon atoms, preferably methyl, an alkoxy of l to 4 carbon atoms,preferably methoxy or a halogen atom, preferably chlorine, morepreferably they are further unsubstituted.

In the compounds of formula I, n may signify l to 10, more preferably 1to 8 and the compounds where n is 3 are still more preferred.

Representative compounds of formula I, include,

those of formula I,

H-I/C j 1" H in which B signifies a radical of formula II or Ila, inwhich K is as defined above,

n signifies l to 8,

R signifies an alkyl radical of l to 4 carbon atoms unsubstituted orsubstituted by a hydroxy, phenyl, (C alkoxy or CONH group,

each of R' and R' which may be the same or different, signifies ahydrogen atom or an alkyl radical of l to 4 carbon atoms, preferablymethyl, and

A is as defined above.

Preferred compounds of formula I, include those of formulae Ia and lb,

C Ia

4 in which R A and n, are as defined above, and K signifies a radical ofthe formula R I N/ 8 in which each of R and R which may be the same ordifferent signifies a hydrogen atom, an alkyl radical of l to 4 carbonatoms, a phenyl or methylphenyl radical or an alkyl radical of l to 4carbon atoms substituted by a chlorine atom, a hydroxy, phenyl, phenoxy,(C alkoxy, phenylcarbonyloxy, phenylaminocarbonyloxyl, (C alkoxycarbonylor (C alkylcarbonyloxy group, with the proviso that when one of R and Rsignifies a phenyl or methylphenyl radical, the other has a significanceother than phenyl or methylphenyl, or,

R and R together with the nitrogen atom to which they are bonded, form apyrrolidine, piperidine, morpholine or piperazine ring,

R signifies a hydrogen or chlorine atom, an alkyl radical of l to 4carbon atoms or an alkoxy radical of l to 4 carbon atoms,

R signifies an alkyl radical of l to 4 carbon atoms or a phenyl radical,and

R is as defined above.

Even more preferred compounds of formula I are those of formulae Ia andId,

(Cl-taken.

in which A is as defined above, R signifies a methyl, ethyl or -C H CONHradical, K" signifies a radical of the formula \R II R 9 \R III --c l Rin which each of R and R which may be the same or different, signifies ahydrogen atom an alkyl radical of l to 4 carbon atoms, a phenyl radical,or an alkyl radical of l to 4 carbon atoms substituted by a chlorineatom, a (C alkoxy, (C alkoxycarbonyl, phenyl, phenoxy,phenylcarbonyloxy, phenylaminocarbonyloxy, (C alkylcarbonyloxy orhydroxy group, with the proviso that when one of R and R signifies aphenyl radical the other has a significance other than phenyl, or,

R and R together with the nitrogen atom to which they are attached, forma morpholine ring, each of,

R and R which may be the same or different, signifies a hydrogen atom,an alkyl radical of 1 to 4 carbon atoms, a phenyl or methylphenylradical, or an alkyl radical of 1 to 4 carbon atoms substituted by a (Calkoxycarbonyl group,

R signifies a hydrogen atom, a methyl or ethyl radical,

R" signifies a methyl or phenyl radical, and

R signifies a hydrogen or chlorine atom, a methyl or methoxy radical.

Suitable organic and inorganic anions A include halide, such aschloride, bromide or iodide, sulphate, bisulphate, methylsulphate,aminosulphonate, perchlorate, carbonate, bicarbonate, phosphate,phosphomolybdate, phosphotungstate, phosphotungstatemolybdate,benzenesulphonate, naphthalenesulphonate, 4-chlorobenzenesulphonate,oxalate, maleinate, acetate, propionate, lactate, succinate,chloroacetate, tartrate, malate, methanesulphonate or benzoate anions orcomplex anions such as that of zinc chloride double salts.

In the compounds of formula I, as defined above, the

- anion A may be exchanged for other anions. This may strates consistingof, or containing homopolymers or copolymers of acrylonitrile orasymmetric dicyanoethylene or for dyeing or printing substrates of acidmodified synthetic polyesters or polyamides. Polyamides of this type aredescribed in Belgian Pat. No. 706,104. Polyesters of this type aredescribed in US. Pat. No. 3,379,723. The substrates may be in loosefibre, yarn or fabric form.

The compounds of formula I may be converted into dyeing preparations,e.g. into stable, liquid or solid dyeing preparations, in conventionalmanner, e.g. by grinding or granulating or dissolving in conventionaldyestuff solvents, if necessary with the addition of an assistant suchas stabilizer. Such preparations may be produced, for example, inaccordance with French Pat. Nos. 1,572,030 and 1,581,900.

Dyeing may be advantageously effected in an aqueous, neutral or acidmedium at a temperature in the range of from 60C to the boiling point orat temperatures over C under pressure.

The dyeings obtained with the compounds of formula I are level, havestable light fastness as well as good wet fastness properties, e.g. towashing, perspiration, sublimation, pleating, decatizing, ironing, steamtreatment, water, sea water, dry cleaning, crossdyeing and solvents. Thedyes are soluble in water, show good compatibility with salt, goodstability to boiling, good pH stability and partially reserve fibresother than those on which they are dyeable.

The compounds, which have good solubility in organic solvents, may alsobe used for dyeing natural or synthetic plastics or resins in the mass;they may be incorporated therein in conventional manner, for example, bymilling, optionally with the use of a solvent.

The compounds are also useful for dyeing leather or paper, e.g. in thestock.

It has been found that mixtures of two or more of the compounds offormula I, or one of the compounds of formula I and other cationic dyescan be used with advantage.

The invention will be further illustrated by the following Exarnples inwhich parts and percentages are by weight and temperatures are indegrees centigrade.

EXAMPLE 1 15.2 Parts of3-amino-5H-6,7,8,9-tetrahydro-striazolo[4,3-a]-azepine are dissolved inparts of 85% formic acid and 15 parts of phosphoric acid and reactedwith 25 parts of a 4N. aqueous sodium nitrite solution at 5 to 10. Thenthe yellow diazo solution is added dropwise to a cold solutionconsisting of parts of diethylaniline, 2 parts of amidosulphonic acid,30 parts of glacial acetic acid and 30 parts of ice. At 5-10 the dyesolution is adjusted to pH 5.5-6.0 with an aqueous sodium hydroxidesolution and stirred for 2 hours. After the addition of 60 parts ofsodium chloride, the dye is filtered, washed with 100 parts of water andvacuum dried at 50.

16.6 Parts of the dried and pulverized dye are mixed with 12 parts of95% ethanol and 125 parts of water. 6.2 Parts of dimethyl sulphate areadded and the solution is heated to 50. The solution is cooled to room,temperature is then extracted 3 times, each time with 150 parts oftrichloroethylene. The aqueous phase is mixed with 3 parts of activatedcharcoal and 3 parts of I-Iyflo. The mixture is filtered and washed with150 parts of water. 5 Parts of zinc chloride are added, on which the dyeis filtered and washed with 30 parts of a 7% aqueous sodium chloridesolution.

On polyacrylonitrile and acid modified polyester the dried dye givesdyeings of fast pink shades.

EXAMPLE 2 15.2 Parts of2-amino-5I-I-6,7,8,9-tetrahydro-striazolo[5,1-a]-azepine are diazotizedas described in Example 1 and coupled to 21 parts ofN-ethyl-N-benzyl-aniline, dissolved in 2 parts of amidosulphonic acid,30 parts of glacial acetic acid and 30 parts of ice. At 5-10 the dyesolution is adjusted to pH 5.5-6.0 with an aqueous sodium hydroxidesolution and stirred for hours. After addition of 60 parts of sodiumchloride the dye is filtered, washed with 100 parts of water and vacuumdried at 50.

18.7 Parts of the dried and pulverized dye are quaternated with dimethylsulphate in accordance with the method described in Example 1 andaccordingly processed.

On polyacrylonitrile and acid modified polyester the dried dye givesdyeings of fast pink shades.

APPLICATION EXAMPLE A 20 Parts of the dye salt described in Example 1 or2 and 80 parts of dextrin are ground in a pulverizing mill for 4 hours.The same dye mixture can be obtained by pasting in 100 parts of waterand subsequent atomizer drying. 1 Part of the resulting preparation ispasted with 1 part of 40% acetic acid, 200 parts of demineralizatedwater are poured in and mixture is boiled for a short time. Then it isdiluted with 7000 parts of demineralizated water, 2 parts of glacialacetic acid are added and at 60 100 parts of polyacrylonitrile fabricare entered into the bath. The fabric can be pretreated for 10-15minutes at 60 in a bath consisting of 8000 parts of water and 2 parts ofglacial acetic acid.

The bath is raised in minutes to 98100 and the fabric boiled for 1 V2hours and rinsed. A pink dyeing is obtained which has good fastness tolight and good wet fastness properties.

10 Parts of the dye salt described in Example 1 or 2, which can beproduced in accordance with the known methods from the corresponding dyehalide or trichlorozincate, are dissolved in 60 parts of glacial acetic8 acid and 30 parts of water. A stable concentrated dye solution isobtained containing about 10% of the dye, which in accordance with theabove dyeing recipe can be used for dyeing polyacrylonitrile.

APPLICATION EXAMPLE B 20 Parts of the dye described in Example 1 or 2and parts of dextrin are mixed in a ball mill for 48 hours. 1 Part ofthe resulting preparation is pasted with 1 part of 40% acetic acid, 200parts of demineralization water are poured in and the mixture is boiledfor a short time. The dyeing with this stock solution is effected asfollows:

a. The solution is diluted with 7000 parts of demineralizated water, 21parts of calcinated sodium sulphate, 14 parts of ammonium sulphate, 14parts of formic acid and 15 parts of a carrier on the basis of reactionproducts of ethylene oxide with dichlorophen- 01s are added and at 60parts of polyester fabric modified with acid groups are entered into thebath. The fabric can be pretreated for 10-15 minutes at 60 in a bathconsisting of 8000 parts of water and 2 parts of glacial acetic acid.

The bath is raised in 30 minutes to 98-100 and fabric boiled for onehour and rinsed. A level pink dyeing is obtained which has good wetfastness properties.

b. The solution is diluted with 3000 parts of demineralizated water, 18parts of calcinated sodium sulphate, 6 parts of ammonium sulphate and 6parts of formic acid are added and at 60 100 parts of polyester fabricmodified with acid groups are entered into the bath. In a closed vesselthe bath is raised in 45 minutes to this temperature is kept for 1 hourwith shaking, then the bath is cooled in 25 minutes to 60 and the fabricis rinsed. A level pink dyeing is obtained which has good wet fastnessproperties.

c. The procedure, described in b. above, is followed, but the bath inthe closed vessel is heated in 1 hour to The structural composition offurther dyes is given in the following Table'I. They can be produced inaccordance with Examples 1 and 2 and agree with the formula CH N where RR R and R have the significances given in the table.

Suitable anions A are those indicated in the above description.

Table I Shade of dyeing 1 15 m u on P y acrylonitrile 3 CH; H -C,H -CHbluish red 4 do. H CH do. yellowish red 5 do. H CH do. bluish red 6 do.H 1 C l-l C H OCH do.

7 (10. H do. c H. 0 db.

8 do. H c,H.o-@ c H.-o red 9 do. H C H C H O-fi bluish red 10 do. C,H CH OCNH bluish red O l 1 do. H do. C H Cl bluish red 12 do. H C H Cl CH.Cl red 13 do. H C H C H C OOC H do. l4 do. H do. C H OH bluish red 15do. H Cl-l ruby l6 do. CH C H C l-l bluish red 17 do. OCH do. cH do.

1 8 do. Cl do. do. scarlet l9 C l-l H do. C H bluish red 20 -C H H C HcH red 21 -C H CONH H do. -C H red 2 la -CH H -CH C H COOC H 1 N- i-CN=NN H H R 014 15 2 (CH I The structural composition of further dyes isgiven in e e 1, 13 R and R have the significances given the followingTable I]. They can be produced in accordance with Examples 1 and 2 andagree with the formula in the table.

Suitable anions A are those indicated in the above description.

Table II Shade of dyeing I R15 R13 RH on polyacrylonitrile 22 cH H C2H5C2H5 bluish red 23 do. H CH CH bluish red 24 do. H CH;, do. bluish red2s do. H C H c H. o-@ do.

26 do. H do. c,H. oI-NH-@ red 27 do. H C H -c H.c1 bluish red 28 do. H-c2H.cl C H Cl red Table ll-continued Shade of dyeing R RI, R RH onpoly- I acrylonitrile 29 do. H CH3 ruby 30 do. CH -C2H C H,, bluish red31 CZH5 H do. do. bluish The structural composition of further dyes isgiven in The structural composition of further dyes is given in thefollowing Table 111. They can be produced in accorthe following TableIV. They can be produced in accordance with Examples 1 and 2 and agreewith the fordance with Examples 1 and 2 and agree with the formula mula1 /13 N i-c N= N A 9 u II N H 13 A R2 0. c--N=N C \N R 1 l R R15 C 3 Z\R where R R R R and Z have the significances where R R R R and Z havethe significances given in the Table III. given in the Table IV.

Suitable anions A are those indicated in the above Suitable anions A arethose indicated in the above description. description.

Table III R, R R R. R5 2 R R R}. Shade of dyeing on polyacrylonitrile 32cH H H H H CH2 -C2H, -c H H bluish red 33 do. H H H H (CH2)2- do. do. Hdo. 34 do. H H H H (CH2)ido. do. H do. 35 do. H H H H (CH do. do. H do.36 do. H H H H (CH2)6 do. do. H do. 37 do H H H H -(CH;).-- do. do. Hdo. 38 do. H H H H -(CH2),. o. do. H do. 39 do. H H H H (CH2),.- do. do.H do. 40 do. H H H H -(CH2),0 do. do. H do. 41 do. H H H H C(CH;,)2 do.do. H do.

42 C H H H H H (cH C H -CH H do.

43 do. H H H H do. do. c. .H-, cH. do. 44 C2H5 H H H H do. do. do. H do.45 c.H.coNH H H H H (CH -C H. c H H bluish red 46 CH;. CH;, H -CH3 H do.do. do. H do. 47 do. do. CH do. --(H;, do do do. H do.

Table IV R R R R R, Z R R R Shade of dyeing on polyacrylonitrile 48 -CHH H H H CH C H C H H bluish red 49 do. H H H H (CH do. do. H do. 50 do.H H H H (CH,),.,-- do. do. H do. 5l C H H H H H CH do. do. H do. 52 C HCONH H H H H do. do. do. H do.

The structural composition of further dyes is given in the followingTable V. They can be produced in accordance with Examples 1 and 2 andagree with the formula where R R R and Z have the significances given inthe table.

Suitable anions A are those indicated in the above description.

1. N+N R H H l6 (9 Na-N N A k R CH iii 7 where R R R and Z have thesignificances given in Table VI the a 9 Shade of Suitable anions A arethose indicated m the above Z Ri R" dyeing on description. polyiacrylo-Ill 1'] e 59 CH;, (c1-| C2H CH reddish Table V violet 60 do. do.C,H,COOC.,H9 do. do. Shade of 61 C H do. c,i-i C H do. R1 Z R"; R"dyeing on polyacrylonitrile A The structural composition of further dyesis given in 53 CH2 C2H5 $2,11 the following Table VII. They can beproduced in ac- 54 do. do. -C2 i 9 do. cordance with Examples 1 and 2and agree with the 55 do. (CH2)2 formula 56 do. -(CH C,H do. do. 57 do.do. C2H4COOC4H9 do. do. 58 C H do. -C,H5 C2H5 do. R

N N II II The structural composition of further dyes is given in C q;the following Table VI. They can be produced in accor- 4 dance withExamples 1 and 2 and agree with the for- 2 l mula Z H N C---N=N o rz G9on N where R, R and Z have the significances given in the table.

Suitable anions A are those indicated in the above description.

Table VII 2 R R Shade of dyeing on polyacrylonitrile 62 (CH -CH3 yellowTable VII-continued Shade of dyeing on polyacrylonitrile brownish red 66(CH do.

bluish red orange reddish yellow red Table VII-continued Z R, R Shade ofdyeing on polyacrylonitrile 75 (CH,);, --cn mqj bluish red C NT? 3 76(Cl-l do. It? scarlet '2: 77 CH do. reddish yellow C H g 78 (CH do. Pdo.

79 -CH do. do. do.

The structural composition of further dyeS is given in 35 where R, R andZ have the significances given in the the folowing Table VI. They can beproduced in accordance with Examples and 2 and agree with the table.

Suitable anions A are those indicated in the above formula description.

40 1|-l1+fi N=N -R C 69 N A9 CH Iil /CH Z TableVIll Shade of dyeing onpoly- Z R R acrylonitrile 80 CH CH yellow C c H 81 (CH do. do. do. 82(CH2):; do. do. do. 83 (CH:);- do. brownish red wa o c 2 H 5 84 (CH CH;;CH reddish yellow (CH2)3-OCH3 Table VIII-continued Shade of dyeixig onpoly- Z R R acrylonitrile 85 (CH,) do. CH 3 do.

On polyacrylonitrile the dyes of the following Examples give dyeingswhich have also good fastness properties.

- ifip 89 Shade CH3 ck E I E N N I 3 blu ish violet G9 (314 Example. 90

CH5 W? T c CN=N O N--/\CH3 bluish violet Example 91 made CH N N l H it 4C C-N=N 0 N 0 bluish red ('9 CH N c H CH 2 (CH2)3 ZnCl 9 Formulae ofrepresentative dyes of the foregoing Examples are as follows:

Example 1' 3 I ZllCl3 N A L-N=N N(C H /CH2 \N/ 2 5 2 CH2 H2 CH2 H2Example 5 on ZnCl CH3. CH N Q Q CH CH Example 22 e C ZnCl 2 3 Example 33e ZnCl 3 ZnCl What is claimed is: 1. A dye of the formula C N Aeor n ,n3 1 I H Q a wherein each of R and R is independently hydrogen, alkyl,phenyl,

cycloalkyl of 5 to 7 carbon atoins, alkylphenyl or alkyl monosubstitutedby halo, phenyl, alkoxy, phenoxy, phenylcarbamoyloxy, alkylcarbonyloxy,alkoxycarbonyl, hydroxy, benzoyloxy or cyano, with the proviso that whenR or R is phenyl, cycloalkyl of 5 to 7 carbon atoms or alkylphenyl, theother is other than phenyl, cycloalkyl of 5 to 7 carbon atoms oralkylphenyl, or

R and R taken together and with the nitrogen atom to which they arejoined are pyrrolidino, piperidino, morpholino or piperazino,

R is hydrogen or alkyl R is alkyl or R is hydrogen or alkyl, each R isindependently hydrogen or alkyl,

R is hydroxy, amino, anilino or anilino monosubstituted or disubstitutedby alkyl,

R is hydrogen, alkyl or alkoxyalkyl,

each X is independently halo, alkyl or alkoxy,

each Y is independently halo, nitro, amino, cyano, thiocyano, hydroxy,alkyl, alkoxy, trifiuoroalkyl, trichloroalkyl, phenyl, phenoxy,alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy,alkylcarbonylamino, alkylsulfonyl, phenylsulfonyl, sulfamoyl,alkylsulfonylamino or phenylsulfonylamino, and

each p is independently O to 2,

A is an anion, and n is l to 10,

wherein each alkyl, alkoxy, alkyl moiety and alkoxy moiety independentlyhas 1 to 4 carbon atoms.

2. A dye according to claim 1 wherein A is zinc trichloride, chloride,acetate or methanesulfonate.

3. A dye according to claim 1 wherein YP N is 9 R P P 4. A dye accordingto claim 1 wherein X is halo, alkyl or alkoxy,

Y is halo, alkyl or alkoxy, and each p is independently or 1. 5. A dyeaccording to claim 4 wherein each p is O.

6. A dye according to claim 4 wherein A is zinc trichloride, chloride,acetate or methanesulfonate.

7. A dye according to claim 4 having the formula wherein R is alkyl oralkyl monosubstituted by hydroxy,

phenyl, alkoxy or carbamoyl, R is hydrogen or alkyl, R, is hydrogen oralkyl, A is an anion, and n is l to 10. 8. A dye according to claim 7having the formula I I R6 7 9. A dye according to claim 8 having theformula wherein R is alkyl or alkyl monosubstituted by hydroxy,

phenyl, alkoxy or carbamoyl,

I R l R9 9 Rl wherein each of R and R is independently hydrogen, alkyl,phenyl,

methylphenyl or alkyl monosubstituted by chloro, hydroxy, phenyl,phenoxy, alkoxy,- benzoyloxy, phenylcarbamoyloxy', alkoxycarbonyl oralkylcarbonyloxy, with the proviso that when R' or R' is phenyl ormethylphenyl, the other is other than phenyl or methylphenyl, or

R' and R' taken together and with the nitrogen atom to which they arejoined are pyrrolidino,

piperidino, morpholino or piperazino, R is hydrogen or alkyl, R is alkylor phenyl, and R is hydrogen, chloro, alkyl or alkoxy,

A is an anion, and n is l to IO.

10. A dye according to claim 9 having the formula wherein R", is methyl,ethyl or 2-carbamoylethyl,

wherein each of R" and R" is independently hydrogen, alkyl, phenyl oralkyl monosubstituted by chloro, alkoxy, alkoxycarbonyl, phenyl,phenoxy, benzoyloxy, phenylcarbamoyloxy, alkylcarbonyloxy or hydroxy,with the proviso that when R" or R is phenyl, the other is other thanphenyl, or

R" and R taken together and with the nitrogen atom to which they arejoined are morpholino, each of R' and R is independenty hydrogen, 10

alkyl, phenyl, methylphenyl or alkoxycarbonylalkyl, with the provisothat when R or R" is phenyl or methylphenyl, the other is other thanphenyl or methylphenyl, R is hydrogen, methyl or ethyl, l R is methyl orphenyl, and R is hydrogen, chloro, methyl or methoxy, and

A is an anion. 11. A dye according to claim wherein R is hydrogen. 2

12. A dye according to claim 11 having the formula 2 I 2 CH ---'CH 2 13.A dye according to claim 12 wherein A is Zncl 15. A dye according toclaim 14 having the formula wherein R, is alkyl or alkyl monosubstitutedby hydroxy, phenyl, alkoxy or carbamoyl,

wherein each of R' and R' is independently hydrogen, alkyl, phenyl,methylphenyl or alkyl monosubstituted by chloro, hydroxy, phenyl,phenoxy, alkoxy, benzoyloxy, phenylcarbamoyloxy, alkoxycarbonyl oralkylcarbonyloxy, with the proviso that when R 8 or R is phenyl ormethylphenyl, the other is other than phenyl or methylphenyl, or

R,; and R,, taken together and with the nitrogen atom to which they arejoined are pyrrolidino, piperidino, morpholino or piperazino,

R is hydrogen or alkyl,

R' is alkyl or phenyl, and

R is hydrogen, chloro, alkyl or alkoxy,

A is an anion, and n is l to 10. i 16. A dye according to claim 15having the formula l CH2:

wherein R" is methyl, ethyl or 2-carbamoylethyl,

31 32 wherein each oi 19. A dye according to claim 18 wherein A is R 8and R 9 is independently hydrogen, alkyl, ZnClgQ phenyl or alkylmonosubstltuted by chloro, alkoxy 20. A dye according to claim 17 havingthe formula alkoxycarbonyl, phenyl, phenoxy, benzoyloxy,

N N H 6B N-- -N A9 CH N CH 2 2 CE\I CH CH 2 phenylcarbamoyloxy,alkylcarbonyloxy or hy- 21. A dye according to claim wherein A is droxy,with the proviso that when R" or R is ZnCI phenyl, the other is otherthan h nyl, o 20 22. A dye according to claim 17 having the formula 2 5C L-N=N 14 /CH? N\ C2K Cl CH CH Gil -"CH R and R" taken together andwith the nitrogen 23. A dye according to claim 17 having the formulaatom to which they are joined are morpholino,

CH 2 4 4 2 Ci, CH CH -T-CH each of R"' and R" is independently hydrogen,24. A dye according to claim 17 having the formula alkyl, phenyl,methylphenyl or alkoxycarbonylal- C kyl, with the proviso that when R"'or R"' is 3 phenyl or methylphenyl, the other is other than N-| phenylor methylphenyl,

R' is hydrogen, methyl or ethyl, R" is methyl or phenyl, and I R' ishydrogen, chloro, methyl or methoxy, and /CH N M 9 A is an anion. CH H17. A dye according to claim 16 wherein R' is hy- \2 j 2 I drogen. CH---CH CH 18. A dye according to claim 17 having the formula 2 2 33 3425. A dye according to claim 24 wherein A is Cl 26. A dye accordin toclaim 17 having the formula I 6 H a C C--N-N N c x -cooc x 2 iz .2 CH CH

1. A DYE OF THE FORMULA
 2. A dye according to claim 1 wherein A is zinctrichloride, chloride, acetate or methanesulfonate.
 3. A dye accordingto claim 1 wherein
 4. A dye according to claim 1 wherein X is halo,alkyl or alkoxy, Y is halo, alkyl or alkoxy, and each p is independently0 or
 1. 5. A dye according to claim 4 wherein each p is
 0. 6. A dyeaccording to claim 4 wherein A is zinc trichloride, chloride, acetate ormethanesulfonate.
 7. A dye according to claim 4 having the formula
 8. Adye according to claim 7 having the formula
 9. A dye according to claim8 having the formula
 10. A dye according to claim 9 having the formula11. A dye according to claim 10 wherein R''16 is hydrogen.
 12. A dyeaccording to claim 11 having the formula
 13. A dye according to claim 12wherein A is ZnCl3 .
 14. A dye according to claim 7 having the formula15. A dye according to claim 14 having the formula
 16. A dye accordingto claim 15 having the formula
 17. A dye according to claim 16 whereinR''16 is hydrogen.
 18. A dye according to claim 17 having the formula19. A dye according to claim 18 wherein A is ZnCl3 .
 20. A dye accordingto claim 17 having the formula
 21. A dye according to claim 20 wherein Ais ZnCl3 .
 22. A dye according to claim 17 having the formula
 23. A dyeaccording to claim 17 having the formula
 24. A dye according to claim 17having the formula
 25. A dye according to claim 24 wherein A is Cl . 26.A dye according to claim 17 having the formula